CN111569882A - Cobaltosic oxide supported copper nano catalyst and preparation method thereof - Google Patents
Cobaltosic oxide supported copper nano catalyst and preparation method thereof Download PDFInfo
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000010949 copper Substances 0.000 title claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 25
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000008367 deionised water Substances 0.000 claims description 39
- 229910021641 deionized water Inorganic materials 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 26
- 239000012279 sodium borohydride Substances 0.000 claims description 21
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 21
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910017816 Cu—Co Inorganic materials 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 229910021642 ultra pure water Inorganic materials 0.000 abstract 1
- 239000012498 ultrapure water Substances 0.000 abstract 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 18
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 14
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 13
- 239000000725 suspension Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
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- 238000000862 absorption spectrum Methods 0.000 description 6
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- 229910001220 stainless steel Inorganic materials 0.000 description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 229940125716 antipyretic agent Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention provides a cobaltosic oxide supported copper nano catalyst and a preparation method thereof, wherein the catalyst is a copper metal catalyst taking cobaltosic oxide as a substrate, which is abbreviated as Cu-Co3O4The main preparation process of the catalyst is as follows: copper nitrate is used as a precursor, and is hydrothermally heated and calcined to form cobaltosic oxide (Co)3O4) A substrate, then adding Co3O4Dispersing in ultrapure water, mixing with reducing agent and copper nitrate solution, and vigorously stirring to deposit copper metal on Co3O4The catalyst synthesized by the method has excellent catalytic performance, and the preparation process is environment-friendly, so that the method has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a cobaltosic oxide supported copper nano catalyst, and a preparation method and application thereof.
Background
The industrial wastewater usually contains a large amount of toxic and difficult-to-degrade substances, which causes serious pollution to the global environment in recent years, and has attracted extensive attention. P-nitrophenol (also known as 4-nitrophenol, abbreviated as 4-NP) is frequently used in various industrial processes as one of the most dangerous contaminants, having adverse effects on the environment and human health due to its toxicity and persistence.
In addition, 4-NP is an important raw material for synthesizing p-aminophenol (4-AP) through a reduction process. 4-AP is an important intermediate in the preparation of analgesics and antipyretics, and has been widely used as photographic developer, corrosion inhibitor, antiseptic lubricant and hair dye, and has great commercial value. Thus, conversion of 4-NP to 4-AP not only eliminates the negative impact on the environment, but also allows access to value-added chemicals.
Sodium borohydride reduction of p-nitrophenol (4-NP) to 4-aminophenol (4-AP) is considered an efficient method for treating 4-NP. The method is simple and convenient to operate, safe and pollution-free, and 4-NP can be completely converted into 4-AP without generating byproducts. However, the reaction is carried out with the addition of a catalyst, and thus, it is of great importance to study a catalyst that can be used for effectively degrading 4-NP.
Co3O4Is black or gray black powder, with Fe3O4The same spinel structure can be regarded as CoO and Co approximately2O3The compound formed. Co3O4The product has stable property, can be slowly dissolved in hot sulfuric acid, but is not dissolved in water, nitric acid and hydrochloric acid at normal temperature. Loss of O at a temperature of above 900 DEG C2Changing into CoO and being easy to be C, CO and H2Reducing the metal into metal.
The noble metal has excellent catalytic performance, but the production cost is too high to be widely applied to wastewater treatment, and the copper nano material is used as a relatively low-cost materialMetals also have catalytic capabilities. Thus, Cu-Co3O4The development and utilization of nanocomposites are feasible.
The invention provides Co successfully constructed with Cu NPs decoration3O4Simple method for making porous sheet materials useful as efficient and stable catalysts for NaBH44-NP hydrogenation reduction as a reducing agent. Co with unique porous structure and high surface area3O4The porous sheet material effectively promotes the dispersion of Cu NP and the formation of an interface electron enhancement region, and provides enough and stable active sites in the catalytic process, so that the 4-NP molecules can absorb electrons to react quickly. These characteristics greatly improve the final catalytic performance of the catalyst.
Therefore, the invention provides the cobaltosic oxide-loaded copper nano catalyst and the preparation method thereof, and the catalyst has the advantages of excellent performance, high stability, low cost and wide application prospect.
Disclosure of Invention
The invention aims to solve the defects of the existing catalyst and provides a cobaltosic oxide-based copper metal supported catalyst and a preparation method thereof, wherein the catalyst takes cobaltosic oxide as a substrate and copper metal nanoparticles as a load, so that the problems of high preparation cost, unstable catalytic performance and the like of the traditional gold catalyst are solved, and the catalyst can play a role in efficient and stable catalysis in the degradation process of dyes such as 4-NP and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
cobaltosic oxide supported copper nano catalyst, abbreviated as Cu-Co3O4The catalyst is Co3O4Copper metal catalyst as substrate, synthesis of Co3O4The precursor of the substrate is cobalt nitrate, and metallic copper is deposited on Co3O4Surface, Cu element and Co3O4The mass ratio is 1: (40-125).
The application also provides a preparation method of the cobaltosic oxide supported copper nano catalyst, which comprises the following steps:
(1) dispersing cobalt nitrate and polyvinylpyrrolidone in deionized water, magnetically stirring for more than 30 minutes, adding quantitative urea, and stirring for more than 30 minutes to obtain a mixed stock solution;
(2) transferring the mixed stock solution obtained in the step (1) to a Teflon-lined autoclave, preserving the temperature at 180 ℃ for more than 10 hours, and naturally cooling to room temperature;
(3) centrifugally separating solid from the mixed stock solution treated in the step (2), sequentially washing with deionized water and alcohol, vacuum-drying for more than 5 hours, and calcining at 500 ℃ for more than 2 hours under the air atmosphere condition to obtain Co3O4A solid powder;
(4) mixing Co3O4Dispersing solid powder in a mixed solvent of deionized water and alcohol, stirring in a water bath for more than 30 minutes, simultaneously adding polyvinylpyrrolidone, a reducing agent and a copper nitrate solution to obtain a catalyst mixed solution, performing ultrasonic treatment for more than 30 minutes, then centrifugally separating out solids, respectively cleaning with deionized water and alcohol, and performing vacuum drying for more than 12 hours to obtain Cu-Co catalyst3O4A catalyst. The water bath is vigorously stirred, so that the metallic copper is deposited on Co3O4A surface.
Preferably, the reducing agent in the step (4) is one or more of sodium borohydride, sodium citrate, hydrazine hydrate, formaldehyde, formic acid, ascorbic acid and ethylene glycol.
Preferably, the reducing agent is prepared by dissolving sodium borohydride in deionized water.
Preferably, in the catalyst mixed solution of step (4), Cu and Co3O4The mass ratio is 1: (40-125).
Preferably, the copper nitrate solution is prepared by dissolving copper nitrate in ethanol.
The invention has the following remarkable advantages:
1) the cobaltosic oxide-loaded copper nano catalyst prepared by the invention has the synergistic effect of copper and cobaltosic oxide in the catalytic process, and can greatly improve the catalytic performance, and the catalyst prepared by the invention is used for catalyzingIn the experiment of reducing 4-NP by using sodium borohydride, the catalyst shows more excellent catalytic performance than the same type of catalyst, and the highest catalytic efficiency is 12.2616min-1。
2) The catalyst adopts lower metal Cu usage amount, the maximum metal Cu usage amount is 2.4 wt%, and the preparation cost is reduced on the premise of ensuring high catalytic performance.
3) Compared with the existing catalyst preparation method, the preparation method adopted by the invention has the advantages of simple and easily-controlled production process, energy conservation, environmental protection, no need of adding other toxic reagents, greenness and no pollution.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern of a sample obtained in example 1.
FIG. 2 is a Transmission Electron Microscope (TEM) image of the sample obtained in example 4.
Fig. 3 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 1.
Fig. 4 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 2.
Fig. 5 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 3.
Fig. 6 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 4.
Fig. 7 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 5.
Fig. 8 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 6.
Fig. 9 is a graph of catalytic efficiency of the catalytic results of examples 1-6 after fitting with a pseudo-first order kinetic model.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
The present invention is further illustrated by the following examples of the invention, but is not limited thereto.
Example 1
1.455g of cobalt nitrate and 0.75g of polyvinylpyrrolidone were weighed out and dissolved in 40mL of deionized water. After magnetic stirring for 30 minutes, 1.2g of urea was added and stirring was continued for another 30 minutes. The mixture was transferred to a Teflon-lined 100mL stainless steel autoclaveKeeping the temperature at 180 ℃ for 10 hours, and naturally cooling to room temperature. The solid is separated by centrifugation, washed by deionized water and alcohol respectively, dried for 5 hours at 60 ℃, then calcined for 2 hours at 500 ℃ in air atmosphere, and the heating rate is 5 ℃/min. Grinding the obtained black solid to obtain the required cobaltosic oxide (Co)3O4)。
0.5g of the above-mentioned cobaltosic oxide powder was weighed in a mixed solvent of 10mL of deionized water and 10mL of ethanol, and then 0.5g of polyvinylpyrrolidone was added while stirring in a water bath at 40 ℃ for 30 minutes. Thereafter, 0.0152g of copper nitrate was weighed into 5ml of ethanol, and the copper nitrate solution was added dropwise to the suspension. Meanwhile, 0.0183g of sodium borohydride is weighed into 3.5ml of deionized water, the sodium borohydride solution is dropwise added into the suspension under vigorous stirring, and ultrasonic treatment is carried out for 30 minutes. Centrifuging to separate out solid, washing with deionized water and alcohol, respectively, drying at 60 deg.C for 12 hr, and labeling with Cu0.8wt％-Co3O4。
Fig. 1 is an X-ray diffraction (XRD) pattern of example 1, and 2 θ ═ 19.0 °, 31.2 °, 36.8 °, 44.8 °, 59.4 ° and 65.2 ° are assigned to Co, respectively3O4(111) Diffraction peaks of crystal plane, (220) crystal plane, (311) crystal plane, (400) crystal plane, (511) crystal plane and (440) crystal plane prove that cobaltosic oxide exists, and no obvious shift of the main peak is observed at the positions, which indicates that the crystal structure of cobaltosic oxide is not changed by deposition of copper; no characteristic diffraction peak of Cu was observed in all samples, indicating that the Cu nanoparticles are very small and highly dispersed on the surface of the tricobalt tetroxide.
FIG. 3 is an image of the catalytic reaction of example 1 under the monitoring of an ultraviolet-visible spectrophotometer (UV-VIS). The whole catalytic reaction is completed within 40 seconds, and the reaction rate (Kapp) after pseudo first-order kinetic model fitting is 8.5698min-1。
Example 2
1.455g of cobalt nitrate and 0.75g of polyvinylpyrrolidone were weighed out and dissolved in 40mL of deionized water. After magnetic stirring for 30 minutes, 1.2g of urea was added and stirring was continued for another 30 minutes. The mixture was transferred to a Teflon-lined 100mL stainless steel autoclave, incubated at 180 ℃ for 10 hours, and allowed to cool naturally toAnd (4) room temperature. The solid is separated by centrifugation, washed by deionized water and alcohol respectively, dried for 5 hours at 60 ℃, then calcined for 2 hours at 500 ℃ in air atmosphere, and the heating rate is 5 ℃/min. Grinding the obtained black solid to obtain the required cobaltosic oxide (Co)3O4)。
0.5g of the above-mentioned cobaltosic oxide powder was weighed in a mixed solvent of 10mL of deionized water and 10mL of ethanol, and then 0.5g of polyvinylpyrrolidone was added while stirring in a water bath at 40 ℃ for 30 minutes. Thereafter, 0.02275g of copper nitrate were weighed into 7.5ml of ethanol, and the copper nitrate solution was added dropwise to the suspension. 0.0275g of sodium borohydride was simultaneously weighed into 5ml of deionized water, and the sodium borohydride solution was added dropwise to the suspension with vigorous stirring and sonicated for 30 minutes. Centrifuging to separate out solid, washing with deionized water and alcohol, respectively, drying at 60 deg.C for 12 hr, and labeling with Cu1.2wt％-Co3O4。
FIG. 4 is an image of the catalytic reaction of example 2 under the monitoring of an ultraviolet-visible spectrophotometer (UV-VIS). The whole catalytic reaction is completed within 120 seconds, and the reaction rate (Kapp) after pseudo first-order kinetic model fitting is 2.6358min-1。
Example 3
1.455g of cobalt nitrate and 0.75g of polyvinylpyrrolidone were weighed out and dissolved in 40mL of deionized water. After magnetic stirring for 30 minutes, 1.2g of urea was added and stirring was continued for another 30 minutes. The mixture was transferred to a Teflon-lined 100mL stainless steel autoclave, incubated at 180 ℃ for 10 hours, and allowed to cool to room temperature. The solid is separated by centrifugation, washed by deionized water and alcohol respectively, dried for 5 hours at 60 ℃, then calcined for 2 hours at 500 ℃ in air atmosphere, and the heating rate is 5 ℃/min. Grinding the obtained black solid to obtain the required cobaltosic oxide (Co)3O4)。
0.5g of the above-mentioned cobaltosic oxide powder was weighed in a mixed solvent of 10mL of deionized water and 10mL of ethanol, and then 0.5g of polyvinylpyrrolidone was added while stirring in a water bath at 40 ℃ for 30 minutes. Thereafter, 0.0266g of copper nitrate was weighed into 9ml of ethanol, and the copper nitrate solution was added dropwise to the suspension. 0.0321g of sodium borohydride were simultaneously weighed into 6ml of deionized waterThe sodium borohydride solution was added drop-wise to the suspension with vigorous stirring and sonicated for 30 minutes. Centrifuging to separate out solid, washing with deionized water and alcohol, respectively, drying at 60 deg.C for 12 hr, and labeling with Cu1.4wt％-Co3O4。
FIG. 5 is an image of the catalytic reaction of example 3 under the monitoring of an ultraviolet-visible spectrophotometer (UV-VIS). The whole catalytic reaction is completed within 40 seconds, and the reaction rate (Kapp) after pseudo first-order kinetic model fitting is 8.0916min-1。
Example 4
1.455g of cobalt nitrate and 0.75g of polyvinylpyrrolidone were weighed out and dissolved in 40mL of deionized water. After magnetic stirring for 30 minutes, 1.2g of urea was added and stirring was continued for another 30 minutes. The mixture was transferred to a Teflon-lined 100mL stainless steel autoclave, incubated at 180 ℃ for 10 hours, and allowed to cool to room temperature. The solid is separated by centrifugation, washed by deionized water and alcohol respectively, dried for 5 hours at 60 ℃, then calcined for 2 hours at 500 ℃ in air atmosphere, and the heating rate is 5 ℃/min. Grinding the obtained black solid to obtain the required cobaltosic oxide (Co)3O4)。
0.5g of the above-mentioned cobaltosic oxide powder was weighed in a mixed solvent of 10mL of deionized water and 10mL of ethanol, and then 0.5g of polyvinylpyrrolidone was added while stirring in a water bath at 40 ℃ for 30 minutes. Thereafter, 0.0304g of copper nitrate was weighed into 10ml of ethanol, and the copper nitrate solution was added dropwise to the suspension. 0.0366g of sodium borohydride was simultaneously weighed into 7ml of deionized water, and the sodium borohydride solution was added dropwise to the suspension with vigorous stirring and sonicated for 30 minutes. Centrifuging to separate out solid, washing with deionized water and alcohol, respectively, drying at 60 deg.C for 12 hr, and labeling with Cu1.6wt％-Co3O4。
FIG. 2 is a Transmission Electron Microscope (TEM) image of the sample obtained in example 4. The figure shows that the cobaltosic oxide substrate is of a sheet structure, and Cu metal is uniformly loaded on the surface of the cobaltosic oxide.
FIG. 6 is an image of the catalytic reaction of example 4 under the monitoring of an ultraviolet-visible spectrophotometer (UV-VIS). The whole catalytic reaction is completed within 30 secondsThe reaction rate after pseudo first order kinetic model fitting (Kapp) was 12.2616min-1。
Example 5
1.455g of cobalt nitrate and 0.75g of polyvinylpyrrolidone were weighed out and dissolved in 40mL of deionized water. After magnetic stirring for 30 minutes, 1.2g of urea was added and stirring was continued for another 30 minutes. The mixture was transferred to a Teflon-lined 100mL stainless steel autoclave, incubated at 180 ℃ for 10 hours, and allowed to cool to room temperature. The solid is separated by centrifugation, washed by deionized water and alcohol respectively, dried for 5 hours at 60 ℃, then calcined for 2 hours at 500 ℃ in air atmosphere, and the heating rate is 5 ℃/min. Grinding the obtained black solid to obtain the required cobaltosic oxide (Co)3O4)。
0.5g of the above-mentioned cobaltosic oxide powder was weighed in a mixed solvent of 10mL of deionized water and 10mL of ethanol, and then 0.5g of polyvinylpyrrolidone was added while stirring in a water bath at 40 ℃ for 30 minutes. Thereafter, 0.0379g of copper nitrate was weighed into 12.5ml of ethanol, and the copper nitrate solution was added dropwise to the suspension. 0.04583g of sodium borohydride was simultaneously weighed into 8.5ml of deionized water, and the sodium borohydride solution was added drop-wise to the suspension with vigorous stirring and sonicated for 30 minutes. Centrifuging to separate out solid, washing with deionized water and alcohol, respectively, drying at 60 deg.C for 12 hr, and labeling with Cu2.0wt％-Co3O4。
FIG. 7 is an image of the catalytic reaction of example 5 under the monitoring of an ultraviolet-visible spectrophotometer (UV-VIS). The whole catalytic reaction is completed within 30 seconds, and the reaction rate (Kapp) after pseudo first-order kinetic model fitting is 8.619min-1。
Example 6
1.455g of cobalt nitrate and 0.75g of polyvinylpyrrolidone were weighed out and dissolved in 40mL of deionized water. After magnetic stirring for 30 minutes, 1.2g of urea was added and stirring was continued for another 30 minutes. The mixture was transferred to a Teflon-lined 100mL stainless steel autoclave, incubated at 180 ℃ for 10 hours, and allowed to cool to room temperature. The solid is separated by centrifugation, washed by deionized water and alcohol respectively, dried for 5 hours at 60 ℃, then calcined for 2 hours at 500 ℃ in air atmosphere, and the heating rate is 5 ℃/min. Obtained black colorGrinding the solid to obtain the required cobaltosic oxide (Co)3O4)。
A mixed solvent of 0.5g of the above cobaltosic oxide powder in 10mL of deionized water and 10mL of ethanol was weighed, and then 0.5g of polyvinylpyrrolidone was added while stirring in a water bath at 40 ℃ for 30 minutes. Thereafter, 0.0455g of copper nitrate was weighed into 15ml of ethanol, and the copper nitrate solution was added dropwise to the suspension. Meanwhile, 0.055g of sodium borohydride is weighed into 10ml of deionized water, the sodium borohydride solution is added into the suspension drop by drop under vigorous stirring, and ultrasonic treatment is carried out for 30 minutes. Centrifuging to separate out solid, washing with deionized water and alcohol, respectively, drying at 60 deg.C for 12 hr, and labeling with Cu2.4wt％-Co3O4。
FIG. 8 is an image of the catalytic reaction of example 6 under the monitoring of an ultraviolet-visible spectrophotometer (UV-VIS). The whole catalytic reaction is completed within 30 seconds, and the reaction rate (Kapp) after pseudo first-order kinetic model fitting is 10.533min-1。
FIG. 9 is a graph comparing catalytic rates of examples 1-6 after fitting to a pseudo-first order kinetic model. As can be seen from the graph, the Cu content increased from 0.8 wt% to 2.4 wt%, and the catalytic rate decreased first and then increased and then decreased, wherein the catalytic rate was the highest at a Cu content of 1.6 wt%.
To summarize the examples and experimental data: according to the cobaltosic oxide-supported copper nano catalyst prepared by the invention, copper and cobaltosic oxide play a synergistic role in a catalytic process, the catalytic performance can be greatly improved, the catalyst prepared by the invention shows more excellent catalytic performance than the same type of catalyst in a sodium borohydride reduction 4-NP (sodium borohydride) catalytic experiment, and the highest catalytic efficiency is 12.2616min-1(ii) a The catalyst adopts lower metal Cu usage amount, the maximum metal Cu usage amount is 2.4 wt%, and the preparation cost is reduced on the premise of ensuring high catalytic performance.
Compared with the existing catalyst preparation method, the preparation method adopted by the invention has the advantages of simple and easily-controlled production process, energy conservation, environmental protection, no need of adding other toxic reagents, greenness and no pollution.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (6)
1. Cobaltosic oxide supported copper nano catalyst, abbreviated as Cu-Co3O4The method is characterized in that: the catalyst is Co3O4Copper metal catalyst as substrate, synthesis of Co3O4The precursor of the substrate is cobalt nitrate, and metallic copper is deposited on Co3O4Surface, Cu element and Co3O4The mass ratio is 1: (40-125).
2. A preparation method of a cobaltosic oxide-supported copper nano catalyst is characterized by comprising the following steps:
(1) dispersing cobalt nitrate and polyvinylpyrrolidone in deionized water, magnetically stirring for more than 30 minutes, adding quantitative urea, and stirring for more than 30 minutes to obtain a mixed stock solution;
(2) transferring the mixed stock solution obtained in the step (1) to a Teflon-lined autoclave, preserving the temperature at 180 ℃ for more than 10 hours, and naturally cooling to room temperature;
(3) centrifugally separating solid from the mixed stock solution treated in the step (2), sequentially washing with deionized water and alcohol, vacuum-drying at 60 ℃ for more than 5 hours, and calcining at 500 ℃ for more than 2 hours under the air atmosphere condition to obtain Co3O4A solid powder;
(4) mixing Co3O4Dispersing solid powder in a mixed solvent of deionized water and alcohol, stirring in a water bath for more than 30 minutes, simultaneously adding polyvinylpyrrolidone, a reducing agent and a copper nitrate solution to obtain a catalyst mixed solution, performing ultrasonic treatment for more than 30 minutes, then centrifugally separating out solids, respectively cleaning with deionized water and alcohol, and performing vacuum drying for more than 12 hours to obtain Cu-Co catalyst3O4A catalyst.
3. The method of claim 2, wherein: and (4) the reducing agent is one or more of sodium borohydride, sodium citrate, hydrazine hydrate, formaldehyde, formic acid, ascorbic acid and glycol.
4. The method of claim 3, wherein the reducing agent is prepared by dissolving sodium borohydride in deionized water.
5. The method according to claim 2, wherein in the catalyst mixed solution of step (4), Cu and Co are contained3O4The mass ratio is 1: (40-125).
6. The method of claim 2, wherein the copper nitrate solution is prepared by dissolving copper nitrate in ethanol.
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